Solids

Ch.13

Solids
Fixed, immobile (so to speak) Symmetry Crystals So whats the inner order?

Unit Cells
Unit cell = smallest repeating unit
containing all symmetry characteristics Unit cell reflects stoichiometry of solid Several unit cell types possible, but atoms or ions placed at lattice points or corners of geometric object

Crystal Lattices

3D unit cells built like legos Crystal Lattice = arrangement of units cells seven 3D units cells found Simplest = Cubic Unit Cell (equal length edges meeting at 90 angles)

Each face part of 2 cubes Each edge part of 4 cubes Each corner part of 8 cubes

Cubic Unit Cell

3 types: 1) Primitive or Simple Cubic (SC) 2) Body-Centered Cubic (BCC) 3) Face-Centered Cubic (FCC)

Cubic Unit Cell (cont.)

Similarity: Same ions/atoms/molecules at each corner Difference: BCC/FCC have more items at other locations BCC has same item in center of cube FCC has same item centered on each side of cube

What do they look like?

SC:
BCC:

FCC:

Which metals have which crystal lattices?

Simple cubic: Po BCC: GI, 3B, 4B, Ba, Ra, Fe FCC: VIIIB, IB, Al, In, Pb

How many atoms per unit cell?

SC: each atom shared by 8 cubes 8 corners of cube 1/8 of each corner
atom w/in unit cell = 1 net atom/unit cell

More on SC
Each atom touches one another along
edge Thus, each edge = 2r Coordination number (# of atoms with which each atom is in direct contact) = 6 Packing efficiency = fraction of volume occupied = 52%

How many atoms per unit cell? (cont.)

BCC: 2 net atoms w/in unit cell (SC + 1
in center)

FCC: 6 faces of cube atom w/in unit

cell = 3 atoms + 1 atom (SC) = 4 net

More on BCC

Each atom does not touch another along edge However, atoms touch along internal diagonal Thus, each edge length = 4r/3 Lets derive this each atom is in direct contact) = 8
Central atom touches 8 atoms

Coordination number (# of atoms with which Packing efficiency = fraction of volume

occupied = 68%

More on FCC

Each atom does not touch another along edge However, atoms touch along face diagonal Thus, each edge length = (22)r Lets derive this

Coordination number (# of atoms with which

each atom is in direct contact) = 12 Packing efficiency = fraction of volume occupied = 74%

Problems
Eu is used in TV screens. Eu has a BCC
structure. Calculate the radius of a europium atom given a MW = 151.964 g/mol, a density of 5.264 g/cm3. Iron has a BCC unit cell with a cell dimension of 286.65 pm. The density of iron is 7.874 g/cm3 and its MW = 55.847 g/mol. Calculate Avogadros number.

CCP and HCP: Efficiency in Stacking

CCP = Cubic Close-Packing (its FCC) HCP = Hexagonal Close-Packing 74% packing efficiency

Structures of ionic solids

Take a SC or FCC lattice of larger ions Place smaller ions in holes w/in lattice Smallest repeating unit = unit cell

CsCl

SC unit cell Cs+ in center of cube Cubic hole Surrounded by 1 Cl- (in 8 parts)
1 Cs+ : 1 Cl-

Coordination # = 8 Why SC and not BCC? Because ion in center different from lattice pt ions

LiCl
Notice: Li+ has octahedral geometry Thus, cation in octahedral hole
(between 6 ions)
Coordination # = 6

FCC

NaCl
FCC Lattice has net 4 Cl-/unit cell
(8x1/8)+(6x1/2) = 4

1 Na+ in center of unit cell 3 Na+ along edges of unit cell

(12x1/4) = 3 Thus, net total of 4 Na+ ions

Total 4 Cl- : 4 Na+ 1:1

Tetrahedral holes
Each ion surrounded by 4 other oppositely
charged ions Unit cell: 4 of each ion total 8 ions Coordination # = 4 8 tetrahedral holes in FCC unit cell
4 by Zn2+ and 4 by S2-

Zn2+ occupies of tetrahedral holes and

surrounded by 4 S2S2- forms FCC unit cell

ZnS

ZnS

Other Types of Solids: Network Solids

Array of covalently bonded atoms Graphite, diamond, and silicon The latter two sturdy, hard, & high
m.p.s

Graphite and diamond

Other Types of Solids: Amorphous Solids

Glass & plastics No regular structure
Break in all sorts of shapes

Long range of m.p.s